The reparation and characterization of cellulose esters LB films with various alkyl chain lengths were studied. Monolayers of cellulose triesters with medium chain length such as trioctanoate(C-8), tridecanoate(C-10), and tridodecanoate(C-12), exhibited a characteristic phase transition from expanded to condensed states. The mechanism of phase transition was discussed on the basis of the temperature dependence of the surface $pressure-area(pi-A)$ isotherms. By the horizontal dipping method, X-type multilayers of cellulose esters were prepared and characterized using the contact angle and XPS spectra.